Treatment of textile and other materials



Patented Oct. 15, 1935 UNITED STATE TREATMENT OF TEXTILE AND QTHERMATERIALS George Holland Ellis and Ernest William Kirk, Spondon, nearDerby, England, assignors to Celanese Corporation of America, acorporation of Delaware No Drawing. Application February 4, 1932, Serial24 Claims.

This invention relates to improvements in the treatment of materials andmore especially to a treatment of textile or other materials to rendercolorations thereon more fast. I

In the coloration of textile and other materials it is of coursedesirable that the colors produced should be as fast as possible tolight and other agencies, for example to the combined action of lightand acid, e. g. acid fumes. Among dyestuffs suffering from a lack offastness to the combined agencies of light and acids, but which areotherwise of great value for the coloration of organic derivatives ofcellulose are certain anthraquinone dyes, particularly those containingfree amino or alkyl amino groups. Some of these dyestuffs yield oncellulose esters and ethers valuable shades, particularly blue shades,which are difiicult to secure by other means and it is therefore amatter of great importance that an eflicient method of increasing thefastness of these dyes in particular should be found.

In U. S. Patent No. 1,723,230 processes are described for increasing thefastness to light of colorations, and particularly azo dye colorations,on materials containing cellulose acetate, by treating the dyed, printedor stencilled materials with one or more amino or substituted aminocompounds, e. g. aniline, alkylated aniline, or alkylated phenylenediamines. Further in U. S. application S. No. 449,082 (Patent 1,930,232)filed 1st May, 1930 there is described the use for the same purpose ofsubstantiallycolorless or white alkylated amino diaryl bases, such forexample as tetramethyl diaminodiphenyl methane or other tetra-alkylateddiaminodiphenyl m e t h a n e 5. Again U. S. application S. No. 523,940filed 19th March, 1931 describes the use of aralkylated aromatic amines,such for example as benzyl-ethylaniline, for increasing the fastness ofcolorations to the combined agencies of light and acid, while in U. S.application S. No. 523,941 (Patent No. 1,957,493) filed 19th March, 1931mono acidyl derivatives of aliphatic diamines are described as usefulfor this purpose.

It has now been found that aralkylamino bases and other organic bases inwhich an amino group In Great Britain February 11,

for example dyeings, printings, or stencillings, produced on celluloseester or ether materials with the above-mentioned anthraquinonederivatives, particularly those containing free amino or alkyl aminogroups, and that compounds of the aforesaid character possess theadvantage of a greatly reduced liability to develop color on exposure toair or oxidizing agencies. These compounds may therefore be used'withoutdanger for increasing the fastness of light colorations which 10 wouldreadily show any discoloration due to the development of color by thestabilizing agent. It has further been found that the aforesaidcompounds may impart other desirable properties to textile materials.Thus higher aliphatic 15 amino bases may be utilized inplace of oils,fats and the like for softening, lubricating and other treatments oftextile materials. The treatments may be applied at any stage in theproduction of these materials. Thus the entire manufacture and treatmentof textile materials from the pro-, duction of the filaments inartificial materials, or the production of yarn in natural materialsright up to the production of finished fabrics, may be effected withoutthe use ofv substances such as fats or oils, liable to develop aciditywhich may be prejudicial to any colorations applied to the materials.

Broadly therefore the present invention comprises treating textilematerials with or incor- 3o porating therein aralkylamino compounds, e.g. primary,secondary, or tertiary aralkylamines, or f other organicamino compounds in which an amino group is not directly attached to anaryl residue. Such compounds are preferably of low volatility. Aminocompounds of the type men-.- tioned and containing more than one aminogrouping also lie within the scope of the present invention.

Among aralkylamino compounds which may be 40 employed in accordance withthe present invention may be mentioned mono-, diand tri-benzylamines,mono benzylmethylamine, di-benzyl-r methylamine,di-beimyl-w-oxy-ethylamine and compounds of this type substituted inaryl nuclei. 45 Among other compounds which may be employed inaccordance with the present invention both for the stabilization ofcolorations and for lubricating, softening and otherwise, treatingtextile materials are aliphatic amines, especially the higher 50aliphatic amines, e. g. those containing 8, 10, 14 or more carbon atoms,for example primary or secondary octylamine, amino derivatives of cycloparafiins or substituted cyclo paraflins, and compounds obtainable bythe action of ammonia or ammonia-yielding compounds on halogenatedhigher aliphatic hydrocarbons. Amines of low volatility are particularlyvaluable.

When applying the invention for improving the fastness of colorations ontextile materials other substances capable of improving their fastness,for instance the ureas, thioureas and guanidines of U. S. application S.No. 450,308 (Patent No. 1,985,248) filed 6th May, 1930, and also thecompounds mentioned in the prior specifications referred to, with orwithout inorganic compounds having an alkaline reaction, that is to say,substances such for example as sodium carbonate, borax, disodiumhydrogen phosphate, sodium acetate, sodium palmitate, or sodium oleatecontaining an inorganic base, may be applied to the materials inaddition to, and either separately from or simultaneuosly with, theamines of the present invention. In the treatment of materials made ofor containing cellulose esters such inorganic substances are preferablynot sufiiciently basic or alkaline, or are not applied in s ufiicientconcentration to produce a deleterious degree of hydrolysis on thecellulose ester.

The amines of the present invention may be applied in any suitablemanner, for example in the treatment of materials containing a celluloseester or ether they may be absorbed from aqueous solutions of theirsalts, for example their hydrochlorides. The cellulose derivative may ifde sired absorb the amine while in a swollen condition. The amines mayalso conveniently be applied in the form of aqueous emulsions ordispersions produced in any suitable manner, for instance by the methodsdescribed in U. S. Patents Nos. 1,618,413, 1,618,414, 1,694,413,1,690,481, 1,803,008 and 1,716,721 and U. S. applications S. Nos.134,138 (Patent No. 1,840,572) filed 7th September, 1926, 390,423(Patent No. 1,928,647) and 390,424 (Patent No. 1,959,352) both filed 4thSeptember, 1929. Again, where possible the amino base may be applied insolution, for example an aqueous solution of monobenzylamine may beapplied to the fabric. From the point of view of ease of application,and capacity for resisting removal from the materials, the inventionparticularly contemplates the use of bases having a substantive affinityfor the materials under treatment.

Emulsions and dispersions of the amines may be directly prepared of astrength suitable for application to the textile materials. If desired,however, the amines may first be brought-into the form of solid,powdered, paste, liquid or other more or less concentrated prepartionscapable of yielding, by dilution with water, soap solution, or the like,treatment baths containing the amino compounds in suitably dispersedform. These preparations which constitute an important feature of thepresent invention may be prepared for instance by evaporating orotherwise removing water from less concentrated preparations or bysimple grinding or mixing the amino compounds with dispersing agentsand/0r protective colloids with or without water. Again, their salts,for example the hydrochlorides, may be ground or mixed with dispersingagents and/or protective colloids whereby preparations may be obtained.

which yield very satisfactory dispersions on discontaining the aminobase together with coloring matters, and particularly the coloringmatters of the anthraquinone series containing free amino or alkyl aminogroups. Such compositions which preferably contain the amino base andthe dyestuff in dispersed form also form part of the present invention,and may be applied directly for the coloration of materials in fastshades.

The bases utilized in accordance with the present invention may beapplied to or incorporated in textile or other materials at any suitablestage of their manufacture. For example, textile materials may betreated with emulsions, dispersions or solutions of the bases before orduring dyeing or during a finishing operation or other aftertreatment;

A further method of incorporating the amino base in artificialmaterials, and particularly artificial materials made of or containingcellulose acetate or other cellulose esters or ethers, consists indissolving or otherwise incorporating the amino base in the spinningsolution used in the manufacture of the materials. Thus, for example anacetone solution of cellulose acetate containing 2% of dibenzylarnine onthe weight of the cellulose acetate may be spun according to dryspinningmethods to produce cellulose acetate u filaments which are capable ofbeing directly dyed in fast shades with anthraquinone dyestuffs. Again,for lubricating, softening or other treatments, the bases mayconveniently be applied to artificial filaments as a solution in avolatile solvent or as an emulsion or dispersion or even in the absenceof other admixture, by means of a wick or like means continuously withtheir production.

The following examples illustrate the invention without being in any waylimitative:-

Example 1 perature kept at C. until the bath is suflid cientlyexhausted. The fabric is then lifted, rinsed and finished. A blue colorof good resistance to the combined action of light and acids is obtainedon the fabric.

Example 2 kilos of a mixed fabric containing approximately 50% cottonand 50% cellulose acetate are immersed in a dye bath of suitable volumecontaining 500 grams of a good textile soap and dispersions of 250 gramsof 1:4-diamethylamino anthraquinone and 250 grams of2:4-dinitro-diphenylamine. One kilo of a dispersion in 50% Turkey redoil of the crude mixture of benzylamines obtained by treating benzylchloride with a solution of ammonia in alcohol for several days at roomtemperature is added together with suitable dyestuifs for the cotton,e.g. Solar Green BL and Solar Flavine 3G (Sandoz) and the temperature ismaintained at 75 C. until the desired shade has been achieved on bothconstituents of the material. The fabric is then lifted, rinsed anddried or otherwise treated as desired. A green shade is obtained whichis of greater fastmess to the action of light and acids than the shadeobtained by a corresponding process wherein there has been no treatmentwith the benzylamines.

Example 3 A concentrated preparation of dibenzylmethylamine prepared bythe action of benzyl chloride on methylainine in alcoholic solution ismade up by stirring 10 kilos of dibenzylmethylamine into 10 kilos of hot50% Turkey red oil. Four kilos of this preparation are then added to adye bath in which 100 kilos of a fabric consisting of cellulose acetateis immersed. Monomethyl-diaminoanthrarufin is then added and the dyeingconducted in the usual manner until the desired shade is achieved. Thefabric is then rinsed, dried, or squeezed free from superfluous liquorand immersed in a bath containing 2 grams per litre each of borax andthiourea. It is then dried without rinsing and finished as desired. Theincorporation of the benzylmethylamine and of the borax and thioureaenhances the resistance of the 1 blue color obtained on the material tothe action of light and to the products of the combustion of coal andcoal gas.

Example 4 1 kilo of secondary octylamine is mixed with 1 kilo of 50%Turkey red oil, the stirring being continued until a homogeneous productis obtained. Cellulose acetate yarn dyed blue-violet with 0.5%1-methylamino-4-amino-anthraquinone is immersed in a bath containing 6grams of the mixture for each litre of its volume and worked untilthoroughly impregnated. The material is then removed and dried withoutrinsing.

As already indicated the invention is of particular value in renderingfast to the combined agencies of light and acid colorations producedwith anthraquinone derivatives, and especially those containing freeamino, or alkyl amino groups. For this reason the process is mostvaluable in connection with treatment of materials made of or containingcellulose acetate or other cellulose esters or ethers, for instancecellulose formate, cellulose propionate, cellulose butyrate, or methyl,ethyl, or benzyl cellulose, or materials containing such cellulosederivatives associated with other fibres, such as wool, cotton, or silk.The invention may, however, be applied to the treatment of materialsconsisting wholly of wool, cotton, or silk or other fibres.

What we claim and desire to secure by Letters Patent is:-

1. Process for improving the fastness of colorations on textilematerials, comprising incorporating in the materials a substantiallycolorless organic compound containing a basic amino group directlyattached to an alkyl group, said compound being free from basic aminogroups attached directly to aryl residues.

2. Process for improving the fastness of colorations on materialscomprising an organic derivative of cellulose, comprising incorporatingin the materials a substantially colorless organic compound containing abasic amino group directly attached to an alkyl group, said compoundbeing free from basic amino groups attached directly to aryl residues.

3. Process for improving the fastness of colorations on materialscomprising cellulose acetate, comprising incorporating in the materialsa substantially colorless organic compound containing a basic aminogroup directly attached to an alkyl group, said compound being free frombasic amino groups attached directly to aryl residues.

4. Process for improving the fastness oi colorations on textilematerials, comprising incorporating in the materials substantiallycolorless aral- 5 kylamines.

5. Process for improving the fastness oi colorations on materialscomprising an organic derivative of cellulose, comprising incorporatingin the materials substantially colorless aralkylamines. 10

6. Process for improving the fastness of colorations on materialscomprising cellulose acetate, comprising incorporating in the materialssubstantially colorless aralkylamines.

7. Process for improving the fastness of colora- 15 tions on materialscomprising an organic derivative of cellulose, comprising incorporatingin the materials up to 2% of their weight of a substantially colorlessaralkylamine.

8. In a process for improving the fastness of 20 colorations on textilematerials comprising an organic derivative of cellulose by means ofsubstantially colorless aralkylamines, incorporating said aralkylaminesin a solution of the cellulose derivative and spinning the solution toform filaments. 25

9. In a process for improving the fastness of colorations on textilematerials comprising cellulose acetate by means of substantiallycolorless aralkylamines, incorporating said aralkylamines in a solutionof the cellulose derivative and spin- 30 ning the solution to formfilaments.

10. Process for improving the fastness of colorations on materialscomprising an organic derivative of cellulose, comprising incorporatingin the materials substantially colorless aralkyl- 5 amines and inorganicsubstances having an acid reaction.

11. Process for improving the fastness of colorations on textilematerials, comprising incorporating in the materials a benzylamine. 40

12. Process for improving the fastness of colorations on materialscomprising an organic derivative of cellulose, comprising incorporatingin the materials a benzylamine.

13. Process for improving the fastness of color- 5 ations on materialscomprising cellulose acetate, comprising incorporating in the materialsa benzylamine.

14. Process for improving the fastness of colorations on materialscomprising cellulose acetate, 50 comprising incorporating in thematerials up to 2% of their weight of a benzylamine.

15. Textile materials containing a substantially colorless organiccompound containing a basic amino group directly attached to an alkylgroup, said compound being free from basic amino compounds directlyattached to aryl residues.

16. Materials comprising an organic derivative of cellulose andcontaining a substantially colorless organic compound containing a basicamino group directly attached to an alkyl group, said compound beingfree from basic amino compounds directly attached to aryl residues.

17. Textile materials containing a substantially colorless aralkylamine.

18. Materials comprising an organic derivative of cellulose andcontaining a substantially colorless aralkylamine.

19. Materials comprising cellulose acetate and containing asubstantially colorless aralkylamine.

20. Materials comprising an organic derivative of cellulose andcontaining up to 2% of their weight of a substantially colorlessaralkylamine.

21. Materials comprising cellulose acetate and containing a benzylamine.

22. A composition 01' matter containing a dyestuff, a substantiallycolorless organic compound 5 containing a basic amino group directlyattached to an alkyl group, said compound being free from basic aminogroups attached to aryl residues, and

a compound selected from the group of dispersing agents and protectivecolloids.

23. A composition or matter containing an GEORGE HOLLAND EILIS. ERNESTWILLIAM KIRK.

